Coating Thickness Determination Using X-ray Fluorescence Spectroscopy: Monte Carlo Simulations as an Alternative to the Use of Standards

X-ray fluorescence is often employed in the measurement of the thickness of coatings. Despite its widespread nature, the task is not straightforward because of the complex physics involved, which results in high dependence on matrix effects. Thickness quantification is accomplished using the Fundamental Parameters approach, adjusted with empirical measurements of standards with known composition and thickness. This approach has two major drawbacks: (i) there are no standards for any possible coating and coating architecture and (ii) even relying on standards, the quantification of unknown samples requires the precise knowledge of the matrix nature (e.g., in the case of multilayer coatings the thickness and composition of each underlayer). In this work, we describe a semiquantitative approach to coating thickness measurement based on the construction of calibration curves through simulated XRF spectra built with Monte Carlo simulations. Simulations have been performed with the freeware software XMI-MSIM. We have assessed the accuracy of the methods by comparing the results with those obtained by (i) XRF thickness determination with standards and (ii) FIB-SEM cross-sectioning. Then we evaluated which parameters are critical in this kind of indirect thickness measurement.